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Publication numberUS4867780 A
Publication typeGrant
Application numberUS 07/214,348
Publication dateSep 19, 1989
Filing dateJul 1, 1988
Priority dateJul 1, 1988
Fee statusLapsed
Also published asDE68917545D1, DE68917545T2, EP0349282A1, EP0349282B1
Publication number07214348, 214348, US 4867780 A, US 4867780A, US-A-4867780, US4867780 A, US4867780A
InventorsFrank X. Woolard
Original AssigneeIci Americas, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Pre- and postemergence herbicides
US 4867780 A
Abstract
Herbicidal compounds have the formula ##STR1## in which W is oxygen or sulfur; X is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl, trifluoromethylsulfonyl, phenoxy, pyridyloxy, halo-substituted-phenoxy or -pyridyloxy, trifluoromethyl-substituted-phenoxy or -pyridyloxy, C1 -C4 alkyloximinomethyl, benzyloximinomethyl, 1-(C1 -C4 alkyl)-oximinoethyl and 1-benzyloximinoethyl; Y is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl and trifluoromethylsulfonyl; Z is hydrogen or fluoro if Y is hydrogen, or hydrogen if Y is other than hydrogen; R1 is hydrogen, methyl, ethyl or chloromethyl; A is oxygen, sulfur, ##STR2## in which R3 and R4 are independently hydrogen, methyl or methoxy; and R2 is alkyl; carboalkoxy; carboalkoxyalkylene; haloalkyl; alkoxy; optionally methylsubstituted cycloalkyl; phenyl; substituted phenyl; phenoxy; halophenoxy; styryl; p-chlorophenylsulfonyl; haloalkylcarbonyl; napthyl; halonapthyl; benzoyl; halo-substituted benzyl; polycyclic aliphatic; mono- or dialkylamino; benzoyl; or a 5- to 6-member heterocyclic ring containing 1-2 oxygen or sulfur atoms, optionally substituted; and m is 0 or 1.
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Claims(35)
What is claimed is:
1. A compound having the formula ##STR20## in which W is oxygen or sulfur;
X is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl, trifluoromethylsulfonyl, phenoxy, pyridyloxy, halo-substituted-phenoxy or -pyridyloxy, trifluoromethyl-substituted-phenoxy or -pyridyloxy, C1 -C4 alkyloximinomethyl, benzyloximinomethyl, 1-(C1 -C4 alkyl)oximinoethyl and 1-benzyloximinoethyl;
Y is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl and trifluoromethylsulfonyl;
Z is hydrogen or fluoro if Y is hydrogen, or hydrogen if Y is other than hydrogen;
R1 is hydrogen, methyl, ethyl or chloromethyl;
A is oxygen, sulfur, ##STR21## in which R3 and R4 are independently hydrogen, methyl or methoxy; and
R2 is C1 -C6 alkyl; carbo(C1 -C6)-alkoxy; carbo(C1 -C6)alkoxy(C1 -C2 alkylene); C1 -C4 haloalkyl if m is 1; C2 -C4 haloalkyl if m is 0; C1 -C5 alkoxy; C3 -C6 cycloalkyl optionally substituted by up to 2 methyl groups; C2 -C6 alkenyl; phenyl; substituted phenyl in which the substituents are C1 -C4 alkyl, halogen, trifluoromethyl, nitro, C1 -C4 alkoxy, C1 -C4 alkylthio, or cyano; phenoxy; halosubstituted phenoxy; styryl; p-chlorophenylsulfonyl; C2 -C4 haloalkylcarbonyl; naphthyl; benzoyl; halosubstituted benzoyl; a polycyclic aliphatic group having from 6 to 12 carbon atoms; amino; mono- or di-(C1 -C4)alkylamino; C3 -C8 alkynyl; cyano; benzyl; or a saturated or unsaturated heterocyclic ring containing from 5 to 6 atoms including from 1 to 2 hetero atoms selected from oxygen and sulfur, optionally substituted by from 1 to 3 methyl groups and/or from 1 to 2 oxo groups; and
m is 0 or 1;
provided that:
(a) when A is --NH-- and R2 is phenyl or substituted phenyl, then W is oxygen; and
(b) when A is oxygen and R2 is substituted phenyl, the substituents on the phenyl ring are not meta-directing electron-withdrawing groups; and
(c) when R2 is cyano or C3 -C8 alkynyl and m is 1, then A is --CH2 --.
2. A compound according to claim 1 in which Y and Z are hydrogen.
3. A compound according to claim 1 in which X is halo, nitro, perhalomethyl, di- or trifluoromethoxy, difluoromethyl or tetrafluoroethoxy.
4. A compound according to claim 3 in which Y and Z are hydrogen.
5. A compound according to claim 1 in which Y is hydrogen and Z is fluoro.
6. A compound according to claim 1 in which Y is 5-halo or 5-trifluoromethyl.
7. A compound according to claim 1 in which m is 0.
8. A compound according to claim 7 in which R2 is C1 -C6 alkyl, C2 -C6 alkenyl, C2 -C4 haloalkyl, C3 -C6 cycloalkyl, C1 -C6 carboalkoxy, C1 -C6 carboalkoxy-(C1 -C2)-alkylene, di-C1 -C4 alkylamino or a 5- to 6-membered saturated or unsaturated heterocyclic ring containing from 1 to 2 oxygen or sulfur atoms.
9. A compound according to claim 1 in which m is 1 and Z is oxygen, sulfur, CH2 or --NH--.
10. A compound according to claim 9 in which R2 is C1 -C6 alkyl, C1 -C5 alkoxy, C1 -C6 carboalkoxy; C1 -C6 carboalkoxy-(C1 -C2)-alkylene, C3 -C6 cycloalkyl, halophenoxy, p-chlorosulfonyl, C2 -C6 alkenyl, C2 -C4 haloalkylcarbonyl, halosubstituted phenyl or a 5- or 6-membered saturated or unsaturated heterocyclic ring containing 1 or 2 sulfur or oxygen atoms.
11. A compound according to claim 1 in which W is oxygen; X is trifluoromethyl or halo; Y is hydrogen; Z is hydrogen and R1 is ethyl.
12. A compound according to claim 11 in which R2 is C1 -C6 alkyl, C2 -C6 alkenyl, C1 -C5 alkoxy, C1 -C4 haloalkyl, if m is 1; C2 -C4 haloalkyl is m is 0; C3 -C6 cycloalkyl, di-(C1 -C4 alkyl)amino, halosubstituted phenyl, halo-substituted phenoxy, p-chlorophenylsulfonyl, C2 -C4 haloalkylcarbonyl, C1 -C6 carboalkoxy, C1 -C6 carboalkoxy-(C1 -C2)alkylene or a 5- to 6-membered saturated or unsaturated heterocyclic ring containing 1 or 2 oxygen or sulfur atoms.
13. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is isobutyl.
14. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is isopropyl.
15. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is cyclopropyl.
16. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is 3-tetrahydrofuryl.
17. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is secondary butyl.
18. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is neopentyl.
19. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is 3,3,3-trifluoro-2-methylpropyl.
20. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is --CH2 --; R1 is ethyl and R2 is cyclopentyl.
21. A compound according to claim 1 in which X is chloro, Y is hydrogen, Z is fluoro, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is isopropyl.
22. A compound according to claim 1 in which X is cyano, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is isopropyl.
23. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is fluoro, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is isopropyl.
24. A compound according to claim 1 in which X is chloro, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is oxygen; R1 is ethyl and R2 is isopropyl.
25. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is --NH--; R1 is ethyl and R2 is ethyl.
26. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is --NH--; R1 is ethyl and R2 is tertiary butyl.
27. A compound according to claim 1 in which X is nitro, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is 0; R1 is ethyl and R2 is isopropyl.
28. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is --CH2 --; R1 is ethyl and R2 is 4-fluorophenyl.
29. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is 1-methylcyclopropyl.
30. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 0; R1 is ethyl and R2 is trans-2-methylcyclopropyl.
31. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is hydrogen, W is oxygen, m is 1, A is oxygen; R1 is chloromethyl and R2 is isopropyl.
32. A compound according to claim 1 in which X is trifluoromethyl, Y is hydrogen, Z is fluoro, W is oxygen, m is 0; R1 is ethyl and R2 is cyclopropyl.
33. An herbicidal composition containing (a) a herbicidally effective amount of a compound according to claim 1 and (b) a herbicidally suitable inert diluent or carrier.
34. A method of controlling undesirable vegetation comprising applying to said vegetation or the locus thereof a herbicidally effective amount of a compound according to claim 1.
35. A method of controlling undesirable vegetation comprising applying to said vegetation or the locus thereof a herbicidally effective amount of a composition according to claim 33.
Description
BACKGROUND OF THE INVENTION

The present invention relates to certain 2-(acylimino)thiazolidine herbicidal compounds, compositions, and methods of use.

There are a number of different types pof herbicides presently sold commercially, and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into or applied to the soil prior to the emergence of the weed plants from the soil, and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil. Some herbicides are effective both as pre- and post-emergence herbicides. The iminothiazolidines of this invention fall into that category.

DESCRIPTION OF THE INVENTION

The compounds of this invention have the formula: ##STR3## in which W is oxygen or sulfur;

X is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl, trifluoromethylsulfonyl, phenoxy, pyridyloxy, halo-substituted-phenoxy or -pyridyloxy, trifluoromethyl-substituted-phenoxy or -pyridyloxy, C1 -C4 alkyloximinomethyl, benzyloximinomethyl, 1-(C1 -C4 alkyl)oximinoethyl and 1-benzyloximinoethyl;

Y is hydrogen, halogen, nitro, cyano, perhalomethyl, difluoromethyl, pentafluoroethyl, C1 -C4 alkyl, C1 -C4 alkoxy, trifluoromethylthio, trifluoromethoxy, tetrafluoroethoxy, methylsulfonyl and trifluoromethylsulfonyl;

Z is hydrogen or fluoro if Y is hydrogen, or hydrogen if Y is other than hydrogen;

R1 is hydrogen, methyl, ethyl or chloromethyl;

A is oxygen, sulfur, ##STR4## in which R3 and R4 are independently hydrogen, methyl or methoxy; and

R2 is C1 -C6 alkyl; carbo(C1 -C6)-alkoxy; carbo(C1 -C6)alkoxy(C1 -C2 alkylene); C1 -C4 haloalkyl if m is 1; C2 -C4 haloalkyl if m is 0; C1 -C5 alkoxy; C3 -C6 cycloalkyl optionally substituted by up to 2 methyl groups; C2 -C6 alkenyl; phenyl; substituted phenyl in which the substituents are C1 -C4 alkyl, halogen, trifluoromethyl, nitro, C1 -C4 alkoxy, C1 -C4 alkylthio, or cyano; phenoxy; halosubstituted phenoxy; styryl; p-chlorophenylsulfonyl; C2 -C4 haloalkylcarbonyl; naphthyl; benzoyl; halosubstituted benzoyl; a polycyclic aliphatic group having from 6 to 12 carbon atoms; amino; mono- or di-(C1 -C4)alkylamino; C3 -C8 alkynyl; cyano; benzyl; or a saturated or unsaturated heterocyclic ring containing from 5 to 6 atoms including from 1 to 2 hetero atoms selected from oxygen and sulfur, optionally substituted by from 1 to 3 methyl groups and/or from 1 to 2 oxo groups; and

m is 0 or 1;

provided that:

(a) when A is --NH-- and R2 is phenyl or substituted phenyl, then W is oxygen; and

(b) when A is oxygen and R2 is substituted phenyl, the substituents on the phenyl ring are not meta-directing electron-withdrawing groups; and

(c) when R2 is cyano or C3 -C8 alkynyl and m is 1, then A is --CH2 --.

The term "alkyl" refers to straight and branched chain acyclic hydrocarbyl moieties having the number of carbon atoms associated with that term whenever used (i.e., by itself or as part of the definition of another moiety, e.g., "haloalkyl", "alkylthio," etc.). Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the various pentyl, hexyl, etc. moieties. The term "iso-C5 H11 " (isoamyl or isopentyl) designates the group 3-methylbutyl. The term "sec-C5 H11 " designates the 2-pentyl group.

The term "carboalkoxy" refers to moieties having the structure ##STR5## in which A represents an alkyl group of the specified number of carbon atoms.

Examples of such group include carbomethoxy, carboethoxy and the like.

The terms "alkenyl" and "alkynyl" refer to straight and branched chain mono- or polyunsaturated acyclic hydrocarbyl moieties with the number of carbon atoms as specified. Examples of such groups include vinyl, allyl, isopropenyl, isobutenyl, propargyl and the like.

The term "cycloalkyl" refers to saturated cyclic hydrocarbyl moieties having the specified number of carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

The term "haloalkyl" refers to an alkyl group having the indicated number of carbon atoms, substituted by one or more halogen atoms, which may be the same or different. When unspecified, the term "haloalkyl" is meant to refer to alkyl groups ranging from monohaloalkyl to fully substituted haloalkyl groups. Examples of haloalkyl groups include chloromethyl, dichloromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, pentafluoroethyl, heptafluoropropyl, 3-chloropropyl, 2,2,2-trifluoro-1-methylethyl, and the like. The term "perhalomethyl" refers to fully halogenated methyl groups such as trifluoromethyl, trichloromethyl, dichlorofluoromethyl and the like.

The heterocyclic rings included in the definition of R2 may be saturated or may be mono- or di-unsaturated. Such rings will contain one or two oxygen or sulfur atoms, for instance, furanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,3-dioxanyl, 1,4-dioxanyl, tetrahydrothienyl, and the like, optionally substituted with from 1 to 3 methyl groups. In addition or alternatively to the methyl substitution, the or two oxygen or sulfur atoms, for instance, furanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,3-dioxanyl, 1,4-dioxanyl, tetrahydrothienyl, and the like, optionally substituted with from 1 to 3 methyl groups. In addition or alternatively to the methyl substitution, the heterocyclic ring may have one or more oxygen atoms doubly bonded to carbon or sulfur atoms in the ring.

Polycyclic aliphatic groups include both bi- and tricyclic groups having the indicated number of carbon atoms, for instance the tricyclic adamantyl group.

When it is indicated that a phenyl ring may be di- or further substituted, the substituents may be the same or different, and are selected from the specified groups. When no specific position of substitution is mentioned on a phenyl ring, it is intended that the substituent or substituents may be substituted at any position on the ring.

However, when A is oxygen, substituents on a phenyl ring for R2 should not be meta-directing electron-withdrawing groups such as nitro or cyano. In such case, the phenyl ring may be substituted with ortho/paradirecting groups (even of the electron-withdrawing type) such as halo, alkoxy and alkyl.

As used herein, the term "herbicide" means a compound or composition which adversely controls or modifies the growth of plants. By the term "herbicidally effective amount" is meant any amount of such compound or composition which causes an adverse modifying effect upon the growth of plants. By "plants" is meant germinant seeds, emerging seedlings and established vegetation, including roots and above-ground portions. Such controlling or modifying effects include all deviations from natural development, such as killing, retardation, defoliation, desiccation, regulation, stunting, tillering, leaf burn, dwarfing, and the like.

The compounds of this invention have been found to be active herbicides, possessing pre- and/or post-emergence herbicidal activity against various types of weeds including broadleaf and grassy weeds. As mentioned below, some of the compounds demonstrate good control of weeds in certain crops such as rice, wheat, corn and cotton.

Therefore this invention also relates to a method for controlling undesirable vegetation in general comprising applying to a locus where control of such vegetation is desired, either prior or subsequent to the emergence of such vegetation, a herbicidally effective amount of a compound as described herein. In another aspect, the invention also relates to herbicidal compositions comprising a herbicidally effective amount of a compound as described herein, together with an inert diluent or carrier suitable for use with herbicides.

The compounds of this invention can be prepared by reaction of a 2-iminothiazolidine with an acylating agent, an isocyanate (when W is oxygen and A is --NH--) or an isothiocyanate (when W is sulfur and A is --NH--) in the presence of a suitable base according to the reaction ##STR6## in which Hal stands for halogen, preferably chlorine or bromine. When an acylating agent is used in this step, the reaction is preferably carried out at a temperature of from about 0 to about 10 C. When an isocyanate or an isothiocyanate is used, the reaction is generally conducted at room temperature under nitrogen or other suitable inert gas.

The starting 2-iminothiazolidines may be prepared according to any of several methods as convenient. For instance, U.S. Pat. No. 4,565,083 discloses several methods for production of compounds of this general type, including cyclization of an isothiocyanate and reaction of an iminothiazolidine with a substituted phenyl fluoride. According to another process, as described in Application Ser. No. 214349 of Frank X. Woolard and Charles Kezerian, entitled "Process for Production of 2-Iminothiazolidines and Oxazolidines", filed concurrently herewith, these intermediates can be prepared by reacting an appropriately substituted phenyl cyanamide in a suitable solvent (for instance toluene or methyl ethyl ketone) with an episulfide and a base according to the reaction ##STR7##

The starting phenyl cyanamides can be made by a number of different methods. These compounds are known in the literature. See, for example, Organic Synthesis, Vol. IV, p. 172 and German Patent Application (OLS) 3,538,128.

The examples which follow illustrate production of compounds of this procedure.

EXAMPLE 1 Preparation of 2-(4-Fluorobenzoylimino)-3-(3-trifluoromethyl)phenyl-5-ethylthiazolidine (Compound 12 herein)

3-Trifluoromethylphenyl cyanamide (62.24 g, 0.334 mol), 1,2-butane episulfide (29.48 g, 0.334 mol) and K2 CO3 (46.16 g, 0.334 mole)along with 500 ml methyl ethyl ketone were combined in a flask equipped with a heating mantle, mechanical stirrer, an reflux condenser equipped with a nitrogen bubbler. The solution was stirred and heated to reflux temperature. After 3 hours, the solution was cooled to room temperature, filtered and the solvent removed in vacuo to give a cloudy oil. The oil was taken up in 300 ml ethyl acetate and washed twice with 200 ml H2 O, and 150 ml saturated NaCl. It was then dried (over Na2 SO4) and the solvent removed in vacuo to give 73.99 g (81%) of product as a clear yellow oil. The product was identified spectroscopically as 2-imino-3-(3-trifluoromethyl)phenyl-5-ethyl thiazolidine.

To a flask equipped with a magnetic stirrer, thermometer and pressure equalizing addition funnel carrying a nitrogen bubbler, was added 2.50 g (9.1 mmol) of the thiazolidine prepared above, 1.27 ml (9.1 mmol) triethylamine and 25 ml of benzene. The solution was stirred and cooled to10 C. Thereafter 1.07 (9.1 mmol) of p-fluorobenzoyl chloride in 10 ml of benzene was added dropwise over a five minute period while the solution was stirred under nitrogen until the addition was complete. The suspension was then washed over 50 ml 3% aqueous HCl, twice with 50 ml water, with 50 ml brine, dried (over MgSO4) and the solvent removed in vacuo to give 3.62 g (100%) of product as a thick pale yellow oil. The oil was identified spectroscopically as the subject compound.

EXAMPLE 2 Preparation of 2-(N-Isopropylcarbamoyl)imino-3-(3-trifluoromethyl)phenyl-5-ethyl thiazolidine (Compound 3 herein)

Two grams (7.3 mmol) of 2-imino-3-(3-trifluoromethyl)phenyl-5-ethylthiazolidine prepared in accordance with the method described in paragraph (1) of Example 1 and 0.72 ml (0.62 g, 7.3 mmol) of isopropyl isocyanate were combined in 30 ml of acetonitrile and stirred overnight under nitrogen at room temperature. Several more drops of the isocyanate were added and the solution stirred for an additional 1.5 hour. The solvent was removed in vacuo to give a yellow-orange syrup that was chromatographed on a silica column in 1:1 ethyl acetate/hexanes to yield 1.41 g (54% of theoretical yield) of product as a caramel colored syrup. The structure was confirmed spectroscopically.

EXAMPLE 3 Preparation of 2-(Isopropoxycarbonyl)imino-3-(3-trifluoromethyl)phenyl-5-ethyl thiazolidine (Compound 4 herein)

To a 500 ml, round-bottomed flask equipped with a stirrer, thermometer, andpressure equalizing addition funnel carrying a nitrogen bubbler was added 18.30 g (66.7 mmol) of 2-imino-3-(3-trifluoromethyl)phenyl-5-ethylthiazolidine prepared in accordance with the method described in paragraph (1) of Example 1 and 200ml of benzene, plus 5.41 ml (5.28 g, 66.7 mmol) pyridine. The contents werecooled to 5 C. with stirring. Thereafter, 7.60 ml (66.7 mmol) of isopropyl chloroformate in 50 ml of benzene was then added dropwise at such a rate that the temperature did not rise above 10 C. (about 18 min.). The stirring was then continued at 5 C. for 0.5 nhour atwhich time gas chromatographic analysis showed the reaction to be complete.The reaction suspension was poured into a separation funnel and washed with4125 ml of water, 1125 ml 3% HCl, 1125 ml brine, dried(over MgSO4) and the solvent removed in vacuo to give 23.18 g (97%) ofproduct was a clear light yellow-orange oil. The structure was confirmed spectroscopically.

Table 1 depicts representative compounds of this invention.

                                  TABLE I__________________________________________________________________________ ##STR8##Cmpd.                                Physical ConstantNo. W X  Y Z R1              A     R2     m.p. C. or__________________________________________________________________________                                nD 301   O CF3    H H C2 H5              (-)   i-C4 H9                                thick syrup2   O CF3    H H C2 H5              NH    CH3    150.0-153.03   O CF3    H H C2 H5              NH    i-C3 H7                                waxy solid4   O CF3    H H C2 H5              O     i-C3 H7                                thick syrup5   O CF3    H H C2 H5              S     i-C3 H7                                102.0-104.06   O CF3    H H C2 H5              CH2                    COOC2 H.sub. 5                                thick syrup7   O CF3    H H C2 H5              (-)   CH3    1.54158   O CF3    H H C2 H5              (-)   CH2 Cl thick syrup9   O CF3    H H C2 H5              (-)   CHCl2  thick syrup10  O CF3    H H C2 H5              CH2                    OCH3   thick syrup11  O CF3    H H C2 H5              (-)                     ##STR9##   waxy solid12  O CF3    H H C2 H5              (-)   2-FC6 H4                                thick syrup13  O CF3    H H C2 H5              (-)   4-FC6 H4                                waxy solid14  O CF3    H H C2 H5              O     CH3    waxy solid15  O CF3    H H C2 H5              O     C2 H5                                1.533616  O CF3    H H C2 H5              (-)   CHCH2  thick syrup17  O CF3    H H C2 H5              (-)   C2 H5                                1.534518  O CF3    H H C2 H5              (-)   CHClCH3                                1.537919  O CF3    H H C2 H5              (-)   CH2 CH2 Cl                                1.539320  O CF3    H H C2 H5              (-)   CHClCH2 Cl                                1.551221  O CF3    H H C2 H5              (-)   CHBrCH2 Br                                thick syrup22  O CF3    H H C2 H5              (-)   C(CH3)CH2                                thick syrup23  O CF3    H H C2 H5              (-)   CHCHCH3                                1.555924  O CF3    H H C2 H5              (-)   CHC(CH3)2                                waxy solid25  O CF3    H H C2 H5              (-)   CH2 CHCH2                                1.574626  O CF3    H H C2 H5              O                     ##STR10##  thick syrup27  O CF3    H H C2 H5              O     CH(CH3)COOCH3                                thick syrup28  O CF3    H H C2 H5              CH2                    OC6 H5                                thick syrup29  O CF3    H H C2 H5              (-)   3-FC6 H4                                waxy solid30  O CF3    H H C2 H5              (-)   CCl3   waxy solid31  O CF3    H H C2 H5              (-)   sec-C4 H9                                1.524232  O CF3    H H C2 H5              (-)   t-C4 H9                                81.0-86.533  O CF3    H H C2 H5              (-)   CH2 C(CH3)3                                1.519134  O CF3    H H C2 H5              (-)   CH(C2 H5)2                                1.525535  O CF3    H H C2 H5              (-)   CH2 CH(CH3)CF3                                1.500336  O CF3    H H C2 H5              (-)   COOC2 H5                                waxy solid37  O CF3    H H C2 H5              (-)                     ##STR11##  waxy solid38  O CF3    H H C2 H5              CH2                     ##STR12##  1.528539  O CF3    H H C2 H5              (-)   CHCHC6 H5 (trans)                                waxy solid40  O CF3    H H C2 H5              CH(CH3)                    OC6 H5                                thick syrup41  O CF3    H H C2 H5              CH2                    O(4-ClC6 H4)                                thick syrup42  O CF3    H H C2 H5              (-)   2-CH3C 6 H4                                90.0-95.043  O CF3    H H C2 H5              (-)   2-ClC6 H4                                97.0-102.044  O CF3    H H C2 H5              (-)   3-ClC6 H4                                thick syrup45  O CF3    H H C2 H5              (-)   4-ClC6 H4                                88.0-95.046  O CF3    H H C2 H5              (-)   3-CF3C 6 H4                                62.0-68.047  O CF3    H H C2 H5              (-)   2,6-FC6 H3                                thick syrup48  O CF3    H H C2 H5              (-)   CH2 Br thick syrup49  O CF3    H H C2 H5              (-)   n-C3 H7                                1.540050  O CF3    H H C2 H5              (-)   C(CH3)2 CH2 Cl                                65.0-69.051  O CF3    H H C2 H5              (-)   CH(CH3)C3 H7                                1.531552  O CF3    H H C2 H5              (-)   C(CH3)2 C3 H7                                1.523853  O CF3    H H C2 H5              (-)   i-C5 H11                                1.525154  O CF3    H H C2 H5              (-)   CHCHC2 H5 (trans)                                1.545155  O CF3    H H C2 H5              (-)                     ##STR13##  1.543856  O CF3    H H C2 H5              (-)   N(C2 H5)2                                71.0-75.557  S CF3    H H C2 H5              (-)   N(CH3)2                                71.0-78.558  O CF3    H H C2 H5              (-)   NH2    foam59  O CF3    H H C2 H5              (-)   COOCH3 75.5-84.060  O CF3    H H C2 H5              O     CH2 CCl.sub. 3                                thick syrup61  O Cl H F C2 H5              O     i-C3 H7                                thick syrup62  O CN H H C2 H5              O     i-C3 H7                                thick syrup63  O CF3    H H C2 H5              O     n-C3 H7                                1.519664  O CF3    H H C2 H5              O     CH2 CH2 Cl                                1.542665  O CF3    H H C2 H5              O     CH2 CH(CH3)2                                1.517066  O CF3    H H C2 H5              O     CH2 CHCH2                                1.536567  O CF3    H H C2 H5              O     n-C4 H9                                1.522068  O CF3    H H C2 H5              O     CH2 CH2 CH2 Cl                                1.535569  O CF3    H H C2 H5              CH2                    O2,4-ClC6 H3                                thick syrup70  O CF3    H F C2 H5              O     C2 H5                                thick syrup71  O Cl H H C2 H5              O     C2 H5                                1.573772  O CF3    H F C2 H.sub. 5              O     i-C3 H7                                thick syrup73  O Cl H H C2 H5              O     i-C3 H7                                1.559274  O CF3    H H C2 H5              O     CCl3   65.0-65.075  O CF3    H H C2 H5              S     C2 H5                                99.0-104.576  O CF3    H H C2 H5              NH    C2 H5                                thick syrup77  O CF3    H H C2 H5              NH    t-C4 H9                                94.0-99.078  O CF3    H H C2 H5              NH    n-C3 H7                                waxy solid79  O CF3    H H C2 H5              NH    CH2 CHCH2                                thick syrup80  O CF3    H H C2 H5              NH    n-C4 H9                                67.0-79.081  O CF3    H H C2 H5              NH    2-FC6 H4                                118.0-130.082  O CF3    H H C2 H5              NH    3-FC6 H4                                101.5-110.083  O CF3    H H C2 H5              NH    4-FC6 H4                                121.5-128.084  O CF3    H H C2 H5              O     sec-C4 H9                                thick syrup85  O CF3    H H C2 H5              O     CH(C2 H5)2                                67.0-73.086  O CF3    H H C2 H5              NH    COCH2 Cl                                102.0-107.087  S CF3    H H C2 H5              NH    t-C4 H9                                107.0-115.088  O CF3    H H C2 H5              S     t-C4 H9                                119.0-125.089  O CF3    H H C2 H5              S     CH3    103.5-107.090  O CF3    H H C2 H5              S     n-C3 H7                                60.0-64.091  O CF3    H H C2 H5              S     CH2 CH2 Cl                                thick syrup92  O CF3    H H C2 H5              S     sec-C4 H9                                99.0-106.593  O CF3    H H C2 H5              S     i-C4 H9                                64.0-72.094  O CF3    H H C2 H5              S     n-C4 H9                                thick syrup95  O CF3    H H C2 H5              S     CH2 CH2 CH2 Cl                                thick syrup96  O CF3    H H C2 H5              S     CH2 CHClCH2 Cl                                thick syrup97  O CF3    H H C2 H5              CH2                    3-CF3C 6 H4                                thick syrup98  O NO2    H H C2 H5              O     i-C3 H7                                thick syrup99  O CF3    H H C2 H5              S     i-C5 H11                                1.5566100 O CF3    H H C2 H5              S     CH2 CH(CH3)CH2 CH3                                51.0-54.0101 O CF3    H H C2 H5              S     n-C5 H11                                1.5549102 O CF3    H H C2 H5              (-)   2-NO2C 6 H4                                106.0-120.0103 O CF3    H H C2 H5              (-)   2-CH3 OC6 H4                                113.0-115.0104 O CF3    H H C2 H5              (-)   3,4,5-CH3 OC6 H2                                thick syrup105 O NO2    H H C2 H5              O     C2 H5                                waxy solid106 O CF3    H H C2 H5              CH.sub. 2                    C6 H5                                60.0-63.0107 O CF3    H H C2 H5              CH2                    4-FC6 H4                                waxy solid108 O CF3    H H C2 H5              O     C6 H5                                thick syrup109 O CF3    H H C2 H5              O     2,4,5-ClC6 H2                                thick syrup110 O CF3    H H C2 H5              O     4-[C(CH3)3 ]C6 H4                                waxy solid111 S CF3    H H C2 H5              NH    C2 H5                                160.5-162.0112 S CF3    H H C2 H5              NH    2-FC6 H4                                112.0-116.0113 S CF3    H H C2 H5              NH    4-FC6 H4                                161.0-166.0114 S CF3    H H C2 H5              NH    3-FC6 H4                                159.0-162.5115 S CF3    H H C2 H5              NH    n-C3 H7                                153.0-156.0116 S CF3    H H C2 H5              NH    i-C3 H7                                130.0-135.0117 O CF3    H H C2 H5              O     cyclopentyl thick syrup118 O CF3    H H C2 H5              CH2                    2-ClC6 H4                                thick syrup119 O CF3    H H C2 H5              CH2                    3-ClC6 H4                                thick syrup120 O CF3    H H C2 H5              CH2                    4-ClC6 H4                                thick syrup121 O CF3    H H C2 H5              CH2                    3,4-ClC6 H3                                thick syrup122 O CF3    H H C2 H5              CH2                    3-FC6 H4                                1.5596123 O CF3    H H C2 H5              CH2                    2-FC6 H4                                thick syrup124 O CF3    H H C2 H5              CH2                    4-CF3C 6 H4                                waxy solid125 O CF3    H H C2 H5              CH2                    2-CF3C 6 H4                                thick syrup126 O CF3    H H C2 H5              CH2                    4-NO2C 6 H4                                76.0-91.0127 O CF3    H H C2 H5              CH2                    3-CH3 OC6 H4                                1.5574128 O CF.sub. 3    H H C2 H5              CH2                    4-CH3 OC6 H4                                1.5574129 O CF3    H H C2 H5              CH(OCH3)                    C6 H5                                waxy solid130 O CF3    H H C2 H5              (-)   α-naphthyl                                thick syrup131 O CF3    H H C2 H5              NH    COC6 H5                                108.0-120.0132 S CF3    H H C2 H5              NH    COC6 H5                                thick syrup133 O CF3    H H C2 H5              NH    CH2 CH2 Cl                                thick syrup134 O CF3    H H C2 H5              O     t-C4 H9                                100.0-105.0135 S CF3    H H C2 H5              NH    2-ClC6 H4                                85.0-95.0136 S CF3    H H C2 H5              NH    3-ClC6 H4                                126.0-132.0137 O CF3    H H C2 H5              NH    3-ClC6 H4                                thick syrup138 S CF3    H H C2 H5              NH    3-CF3C 6 H4                                112.0-119.0139 O CF3    H H C2 H5              NH    2-CH3 OC6 H4                                105.0-111.0140 O CF3    H H C2 H5              NH    3-CH3 OC6 H4                                thick syrup141 O CF3    H H C2 H5              NH    3-CH3 SC6 H4                                glassy solid142 O CF3    H H C2 H5              NH    2,5-FC6 H3                                thick syrup143 O CF3    H H C2 H5              S     4-ClC6 H4 CH2                                waxy solid144 O CF3    H H C2 H5              C2 H4                    COOC2 H5                                1.5285145 O CF3    H H C2 H5              (-)   2-BrC6 H4                                82.0-89.0146 O CF3    H H C2 H5              CH2                    2-CH3C 6 H4                                thick syrup147 O CF3    H H C2 H5              CH2                    2-OCH3C 6 H4                                thick syrup148 O CF3    H H C2 H5              CH2                    2-NO2C 6 H4                                100.0-117.0149 S CF3    H H C2 H5              NH    2-ClC6 H4 CO                                thick syrup150 O CF3    H H C2 H5              NH    4-ClC6 H4 SO2                                glassy solid151 S CF3    H H C2 H5              NH    n-C4 H9                                129.0-138.0152 O CF3    H H C2 H5              --                     ##STR14##  waxy solid153 O CF3    H H C2 H5              --                     ##STR15##  thick syrup154 O CF3    H H C2 H5              CH2                     ##STR16##  1.5670155 O CF3    H H C2 H5              CH2                    2,4-ClC6 H4                                thick syrup156 O CF3    H H C2 H5              CH2                    3-NO2C 6 H4                                95.0-103.0157 O CF3    H H C2 H5              CH2                    3-CH3C 6 H4                                waxy solid158 O CF3    H H C2 H5              CH2                    2,6-FC6 H3                                thick syrup159 O CF3    H H C2 H5              CH2                    2,6-ClC6 H3                                waxy solid160 O CF3    H H C2 H5              NH    CH2 COOC2 H5                                92.0-99.0161 S CF3    H H C2 H5              NH    adamantyl   waxy solid162 O CF3    H H CONCH3              CH3                    C2 H5                                thick syrup163 O CF3    H H C2 H5              CH2                    2,3-(CH3 O)C6 H3                                thick syrup164 O CF3    H H CH2 Cl              O     i-C3 H7                                waxy solid165 O CF3    H H CH3              O     i-C3 H7                                thick syrup166 O CF3    H F C2 H5              (-)                     ##STR17##  waxy solid167 O CF3    H F C2 H5              (-)                     ##STR18##  waxy solid168 O CF3    H H C2 H5              CH2                    2,3-FC6 H3                                thick syrup169 O CF3    H F C2 H5              (-)                     ##STR19##  thick syrup170 O CF3    H H CH2 Cl              (-)   i-C4 H9                                thick syrup171 O CF3    H H CH2 Cl              NH    i-C3 H7                                thick syrup172 O CF3    H H CH2 Cl              S     i-C3 H7                                waxy solid173 O CF3    H H CH3              (-)   i-C4 H9                                thick syrup__________________________________________________________________________(-) Indicates an electron bond, i.e., m = 0.
HERBICIDAL ACTIVITY TESTS

Compounds in Table 1 were tested for herbicidal activity as follows.

The herbicidal effect is observed by comparing the extent of weed control in test flats treated with the compounds against that occurring in similarnon-treated control flats. All were applied at 4.0 lb/A (4.48 kg/ha) to pre-emergence and post-emergence screening flats. An 80 gal/A (748.3 l/ha)spray volume was utilized. Post-emergence flats were seeded 12 days prior to treatment. Pre-emergence flats were seeded one day prior to treatment. Overhead watering of pre-emergence flats and soil surface watering of post-emergence flats, so as to avoid wetting the foliage, were carried outfor the duration of the test.

Weed seeds were planted in a flat at a seed depth of 0.5 inch (1.3 cm). Soil for flats was prepared using loam soil fortified with 17-17-17 fertilizer (N-P2 O5 -K2 O on a weight basis) and Captan 80Wfungicide. The test weeds were as follows:

______________________________________COMMON NAME    SCIENTIFIC NAME ABR______________________________________green foxtail  Setaria viridis SETVIwatergrass     Echinochloa crusgalli                          ECHCGwild oat       Avena fatua     AVEFAannual morningglory          Ipomoea purpurea                          PHBPUvelvetleaf     Abutilon theophrasti                          ABUTHwild mustard   Brassica kaber  SINARyellow nutsedge          Cyperus esculentus                          CYPES______________________________________

The spray solutions were prepared by dissolving 240 mg of test compound in 20 ml of acetone containing 1% polyoxyethylene sorbitan monolaurate emulsifier, then adding 20 ml of water to the resulting solution. The stock solutions were applied using a linear spray table. Pre-emergence flats are raised to the level of the post-emergence foliage canopy by setting the flats on a wooden block.

In both pre- and post-emergent testing, the degree of weed control was visually assessed, approximately 18 days after treatment, and recorded as percentage control compared to the growth of the same species in an untreated check flat of the same age. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated control, and 100 equals complete kill.

The results are listed in the Table below.

                                  TABLE II__________________________________________________________________________GREENHOUSE HERBICIDE TEST RESULTSApplicationCmpd.    Rate     Percent InjuryNo. (lb/A)   Method        SETVI            ECHCG                 AVEFA                      PHPBU                           ABUTH                                SINAR                                     CYPES__________________________________________________________________________1   4.00   PES  100 100  90   100  100  100  30    4.00   POS  100 80   80   80   80   70   802   4.00   PES  100 100  80   100  100  100  70    4.00   POS  95  85   60   75   75   80   803   4.00   PES  100 100  80   100  100  100  70    4.00   POS  90  80   70   50   50   80   804   4.00   PES  100 90   100  100  100  100  80    4.00   POS  100 80   80   80   90   50   805   4.00   PES  100 70   75   100  75   100  0    4.00   POS  80  50   50   90   90   60   06   4.00   PES  10  10   0    5    5    20   0    4.00   POS  10  20   10   10   80   80   07   4.00   PES  100 40   10   0    0    100  0    4.00   POS  20  20   20   0    30   80   08   4.00   PES  100 30   0    10   0    100  0    4.00   POS  20  20   0    10   80   100  09   4.00   PES  100 30   10   10   80   100  0    4.00   POS  20  20   20   10   80   100  010  4.00   PES  100 100  85   60   100  100  60    4.00   POS  100 90   80   40   80   100  7511  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 85   85   100  100  100  8012  4.00   PES  100 100  100  100  100  100  0    4.00   POS  50  50   50   60   85   90   013  4.00   PES  100 30   10   100  100  100  0    4.00   POS  100 50   50   100  90   100  014  4.00   PES  100 100  100  100  100  100  60    4.00   POS  100 100  100  100  85   100  2015  4.00   PES  100 100  95   100  100  100  60    4.00   POS  100 80   80   80   80   100  7516  4.00   PES  100 10   10   40   100  100  0    4.00   POS  0   20   0    20   30   80   017  4.00   PES  100 100  80   10   90   100  0    4.00   POS  100 30   10   10   80   90   018  4.00   PES  100 100  20   90   100  100  0    4.00   POS  20  20   20   100  80   100  019  4.00   PES  100 100  100  100  100  100  0    4.00   POS  100 40   40   30   80   90   020  4.00   PES  100 20   10   20   95   100  0    4.00   POS  10  10   10   10   80   90   021  4.00   PES  80  10   0    10   80   100  0    4.00   POS  0   0    0    10   10   100  022  4.00   PES  100 100  50   80   100  100  0    4.00   POS  100 50   50   100  85   100  3023  4.00   PES  100 100  100  100  100  100  0    4.00   POS  100 80   80   80   80   90   7024  4.00   PES  100 100  100  100  100  100  30    4.00   POS  100 85   90   100  90   100  7525  4.00   PES  100 100  90   100  100  100  0    4.00   POS  100 80   80   100  90   100  3026  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 90   80   100  95   100  8027  4.00   PES  100 50   50   100  100  100  10    4.00   POS  80  50   50   100  100  100  5028  4.00   PES  100 20   10   20   20   100  0    4.00   POS  0   10   0    40   80   90   029  4.00   PES  100 85   80   100  100  100  0    4.00   POS  10  10   10   60   90   100  030  4.00   PES  100 80   60   10   100  100  0    4.00   POS  10  10   10   40   40   80   031  4.00   PES  100 100  100  100  100  100  0    4.00   POS  90  90   90   80   90   90   1032  4.00   PES  100 100  100  100  100  100  10    4.00   POS  100 100  90   80   80   100  033  4.00   PES  100 100  100  100  100  100  20    4.00   POS  100 90   90   80   80   100  7034  4.00   PES  100 100  100  100  100  100  10    4.00   POS  100 80   80   80   80   100  3035  4.00   PES  100 100  100  100  100  100  10    4.00   POS  100 90   90   80   80   100  6036  4.00   PES  100 20   10   30   70   100  0    4.00   POS  10  10   10   20   20   80   037  4.00   PES  100 100  100  100  100  100  0    4.00   POS  50  50   50   60   60   80   2038  4.00   PES  100 100  95   100  100  100  0    4.00   POS  100 80   80   80   80   100  2039  4.00   PES  100 50   20   20   70   100  0    4.00   POS  20  20   20   40   60   80   040  4.00   PES  100 75   30   40   75   100  0    4.00   POS  10  0    0    40   60   80   041  4.00   PES  100 80   30   100  100  100  0    4.00   POS  50  10   0    100  100  100  042  4.00   PES  100 80   70   60   100  100  0    4.00   POS  50  50   50   40   60   60   043  4.00   PES  100 80   60   100  100  100  0    4.00   POS  50  50   50   30   50   80   044  4.00   PES  100 50   30   80   100  100  0    4.00   POS  30  30   30   40   80   80   045  4.00   PES  100 60   30   80   100  100  0    4.00   POS  30  30   30   30   30   80   046  4.00   PES  100 40   30   70   85   100  0    4.00   POS  30  80   30   60   80   80   047  4.00   PES  100 30   10   60   100  100  0    4.00   POS  30  30   30   40   60   80   048  4.00   PES  100 20   0    10   0    100  0    4.00   POS  30  30   30   60   60   80   049  4.00   PES  100 100  95   95   100  100  0    4.00   POS  80  30   60   40   80   80   050  4.00   PES  100 100  80   100  100  100  0    4.00   POS  80  80   60   80   80   80   1051  4.00   PES  100 100  85   100  100  100  0    4.00   POS  100 80   80   90   85   100  3051  4.00   PES  100 100  85   100  100  100  0    4.00   POS  100 80   80   90   85   100  3052  4.00   PES  100 100  30   80   100  100  0    4.00   POS  100 90   80   90   90   90   053  4.00   PES  100 100  80   100  100  100  0    4.00   POS  100 90   80   95   100  100  054  4.00   PES  100 100  50   75   100  100  0    4.00   POS  100 85   50   85   85   100  055  4.00   PES  100 100  95   100  100  100  0    4.00   POS  100 85   80   100  100  100  3056  4.00   PES  100 100  100  100  100  100  0    4.00   POS  100 90   85   80   80   80   6057  4.00   PES  100 100  100  100  100  100  30    4.00   POS  100 100  90   85   90   100  7058  4.00   PES  100 100  90   100  100  100  80    4.00   POS  100 85   80   80   80   100  8059  4.00   PES  100 0    0    10   10   100  0    4.00   POS  0   10   0    20   30   80   060  4.00   PES  100 10   30   0    100  100  0    4.00   POS  10  10   10   20   50   90   061  4.00   PES  100 100  100  100  100  100  70    4.00   POS  100 100  100  90   100  90   8062  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 100  90   100  100  100  8063  4.00   PES  100 100  100  100  100  100  30    4.00   POS  100 90   80   90   90   80   7064  4.00   PES  100 100  80   100  100  100  0    4.00   POS  100 100  80   80   80   80   7065  4.00   PES  100 100  100  100  100  100  0    4.00   POS  100 90   90   80   95   90   7066  4.00   PES  100 90   100  100  100  100  50    4.00   POS  100 80   80   60   80   90   8067  4.00   PES  100 60   40   100  100  100  0    4.00   POS  100 50   50   70   80   90   3068  4.00   PES  100 80   0    100  100  100  0    4.00   POS  100 50   50   60   80   90   5069  4.00   PES  100 80   0    100  80   100  0    4.00   POS  10  10   10   100  100  100  070  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 100  95   75   90   100  9071  4.00   PES  100 100  95   100  20   100  70    4.00   POS  100 100  60   60   80   100  7572  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 90   80   80   80   80   8073  4.00   PES  100 100  100  100  100  100  70    4.00   POS  100 95   95   90   85   100  8074  4.00   PES  100 90   50   20   20   100  0    4.00   POS  50  50   50   60   60   80   2075  4.00   PES  100 100  95   100  100  100  0    4.00   POS  80  60   50   40   80   80   076  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 100  100  90   90   100  8077  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 100  100  100  100  100  8078  4.00   PES  100 100  100  100  100  100  70    4.00   POS  100 90   100  80   80   100  8079  4.00   PES  100 100  100  100  100  100  70    4.00   POS  80  80   80   80   80   80   8080  4.00   PES  100 100  100  100  100  100  70    4.00   POS  80  70   75   80   80   80   8081  4.00   PES  100 50   50   100  100  100  0    4.00   POS  50  50   50   20   50   80   082  4.00   PES  100 60   40   100  100  100  0    4.00   POS  50  50   50   20   60   80   083  4.00   PES  100 30   30   100  100  100  0    4.00   POS  0   0    0    40   80   80   084  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 90   80   80   80   80   8085  4.00   PES  100 100  90   100  100  100  0    4.00   POS  50  60   50   80   80   80   5086  4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 80   60   80   80   80   8087  4.00   PES  100 100  100  100  100  100  70    4.00   POS  100 90   90   80   90   90   8088  4.00   PES  100 80   75   90   100  100  0    4.00   POS  20  20   20   30   30   50   089  4.00   PES  100 100  100  100  100  100  30    4.00   POS  100 80   80   60   80   80   8090  4.00   PES  100 100  100  100  100  100  0    4.00   POS  80  30   60   60   80   90   2091  4.00   PES  100 100  90   100  100  100  0    4.00   POS  100 50   50   60   80   80   8092  4.00   PES  100 30   80   100  100  100  0    4.00   POS  20  20   20   30   50   100  093  4.00   PES  100 50   100  100  100  100  0  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100  70   100  100  100  0    4.00   POS  60  60   60   60   60   100  50116 4.00   PES  100 100  80   100  100  100  0    4.00   POS  80  90   80   80   60   90   80117 4.00   PES  100 100  80   100  100  100  0    4.00   POS  80  90   80   80   80   100  80118 4.00   PES  100 100  80   100  100  100  0    4.00   POS  100 90   70   100  100  100  0119 4.00   PES  100 100  80   100  100  100  0    4.00   POS  100 90   80   80   80   100  0120 4.00   PES  100 100  70   100  100  100  0    4.00   POS  100 95   40   60   80   100  0121 4.00   PES  100 10   10   40   20   100  0    4.00   POS  20  20   20   40   40   80   0122 4.00   PES  100 100  85   100  100  100  0    4.00   POS  100 100  80   90   90   100  0123 4.00   PES  100 100  90   100  100  100  0    4.00   POS  100 100  60   100  100  100  20124 4.00   PES  100 90   20   20   80   100  0    4.00   POS  20  80   20   10   30   100  0125 4.00   PES  100 30   20   40   60   100  0    4.00   POS  100 30   30   60   50   80   0126 4.00   PES  100 10   10   10   20   80   0    4.00   POS  20  20   0    20   20   100  0127 4.00   PES  100 100  75   100  85   100  0    4.00   POS  100 50   30   80   80   100  0128 4.00   PES  100 100  90   100  100  100  0    4.00   POS  100 100  80   60   80   80   0129 4.00   PES  100 40   20   40   80   100  0    4.00   POS  100 30   20   60   50   100  0130 4.00   PES  100 10   10   10   60   100  0    4.00   POS  0   10   0    40   60   100  0131 4.00   PES  100 10   10   10   75   100  0    4.00   POS  20  30   20   80   80   100  0132 4.00   PES  100 20   40   40   60   100  0    4.00   POS  90  50   40   85   80   100  50133 4.00   PES  100 100  20   60   80   85   0    4.00   POS  80  30   30   100  100  85   0134 4.00   PES  100 100  100  80   100  100  0    4.00   POS  100 30   10   100  100  100  0135 4.00   PES  100 20   20   60   100  100  0    4.00   POS  70  20   10   40   100  80   0136 4.00   PES  100 0    0    20   20   50   0    4.00   POS  10  10   0    40   70   80   0137 4.00   PES  100 20   20   80   80   100  0    4.00   POS  75  20   0    60   80   80   0138 4.00   PES  100 0    0    0    0    0    0    4.00   POS  10  10   10   20   30   30   0139 4.00   PES  100 0    10   10   20   20   0    4.00   POS  10  0    0    40   20   50   0140 4.00   PES  100 30   30   75   100  100  0    4.00   POS  10  10   0    40   80   90   0141 4.00   PES  100 20   20   75   20   100  0    4.00   POS  20  10   0    100  90   90   0142 4.00   PES  100 100  75   100  100  100  0    4.00   POS  60  50   30   100  80   80   0143 4.00   PES  80  0    0    0    0    80   0    4.00   POS  10  10   10   10   80   80   0144 4.00   PES  20  0    0    0    0    0    0    4.00   POS  0   0    0    20   50   80   0145 4.00   PES  100 60   30   60   85   100  0    4.00   POS  20  30   20   60   80   80   0146 4.00   PES  100 100  60   85   90   100  0    4.00   POS  80  50   50   80   80   80   0147 4.00   PES  100 100  60   70   100  100  0    4.00   POS  80  50   50   80   80   80   0148 4.00   PES  100 75   20   70   100  100  0    4.00   POS  10  10   10   80   90   90   0149 4.00   PES  100 95   50   40   90   100  30    4.00   POS  80  50   50   80   80   80   30150 4.00   PES  80  0    0    0    10   30   0    4.00   POS  0   0    0    20   60   80   0151 4.00   PES  100 30   30   40   50   100  0    4.00   POS  30  30   20   80   80   80   0152 4.00   PES  100 100  100  100  100  100  30    4.00   POS  100 80   80   80   80   80   0153 4.00   PES  100 100  90   100  100  100  30    4.00   POS  100 80   80   80   80   90   30154 4.00   PES  100 100  85   95   100  100  0    4.00   POS  90  60   50   100  85   100  0155 4.00   PES  100 85   60   85   100  100  0    4.00   POS  60  40   30   80   80   80   0156 4.00   PES  100 20   10   40   70   95   0    4.00   POS  20  20   20   60   60   80   0157 4.00   PES  100 100  80   85   100  100  0    4.00   POS  80  40   30   60   80   80   0158 4.00   PES  100 100  90   100  100  100  0    4.00   POS  100 100  85   85   90   80   0159 4.00   PES  100 100  50   80   100  85   0    4.00   POS  80  30   20   80   85   90   20160 4.00   PES  75  20   0    5    0    0    0    4.00   POS  0   0    0    50   20   100  0161 4.00   PES  100 30   20   20   60   100  0    4.00   POS  70  30   20   40   80   100  0162 4.00   PES  100 60   20   20   0    100  0    4.00   POS  100 0    0    30   40   80   0163 4.00   PES  100 20   10   20   10   100  0    4.00   POS  100 10   10   20   40   85   0164 4.00   PES  100 100  95   100  100  100  20    4.00   POS  100 100  100  100  100  100  70165 4.00   PES  100 100  100  100  100  100  80    4.00   POS  100 95   100  80   80   80   80166 4.00   PES  100 100  100  100  95   100  N    4.00   POS  100 100  100  100  100  100  80167 4.00   PES  100 100  100  100  100  100  0    4.00   POS  100 100  100  90   95   100  20168 4.00   PES  100 100  95   100  95   100  0    4.00   POS  100 70   70   80   80   80   10169 4.00   PES  100 100  95   100  100  100  0    4.00   POS  100 90   100  95   95   100  20170 4.00   PES  100 100  70   100  95   100  90    4.00   POS  100 90   30   90   90   90   0171 4.00   PES  100 100  40   100  100  100  20    4.00   POS  100 100  100  95   100  100  80172 4.00   PES  100 100  30   50   100  100  0    4.00   POS  60  30   20   10   20   80   0173 4.00   PES  100 100  85   100  100  100  0    4.00   POS  100 90   85   90   90   90   0__________________________________________________________________________
FURTHER HERBICIDAL EVALUATION

Compounds showing good activity in the evaluations described above were submitted for one or more subsequent evaluations involving, for example, different weeds, lower application rates, varying application procedures, and/or selectivity with respect to crops. The weeds employed in these tests included those utilized in the tests just described, as well as a number of others such as one or more species of ryegrass (Lolium), Sorghum, signalgrass (Brachiaria), cocklebur (Xanthium), Sesbania, Cassia,Alopecurus, oats (Avena), bluegrass (Poa), Matricaria, chickweed (Stellaria), bedstraw (Galium), and violet Viola). Crops which were variously employed in these evaluations included cotton (Gossypium hirsutum), soybean (Glycine max), corn (Zea maize), milo (Sorghum bicolor), wheat (Tritium aestivum), sugarbeet (Beta vulgaris), rice (Oryzasativa), carrot (Daucus carota), and barley (Hordeum vulgare).

In summation, compounds submitted for further evaluation showed varying activity depending on the compound and the evaluation employed. Some compounds showed a better activity in controlling grasses, others in controlling broadleaf weeds. Some compounds demonstrated better activity in pre-emergence application, others in post-emergence application. Some compounds demonstrated good activity in nearly all types of application. Some compounds demonstrated good control in tests at application rates ranging as low as 0.06 pound per acre (0.065 kg/ha).

With respect to injury to crops, nearly all compounds tested produced unacceptable injury to sugarbeets even at relatively low levels of application. Some compounds showed good broad-spectrum activity but relatively low selectivity, causing injury to both weeds and crops in the same tests. Other compounds showed varying selectivity to certain crops, particularly cereals, such as wheat, rice and corn, most notably with respect to rice in various methods of application. A number of compounds also demonstrated selectivity in controlling weeds in the presence of cotton.

In practice, a pure compound can be used as a herbicide. However, in general, the compounds are first formulated with one or more inert carriers or diluents suitable for herbicidal use, before being applied.

The compositions or formulations, including a compound as described herein,may exist in any one of a number of solid or liquid forms. Examples of solid forms are dusts, granules, tablets, powders and the like. Examples of liquid forms are emulsifiable concentrates, flowables and pastes. Such compositions may contain, in addition to the active compound or compounds,various carriers or diluents; surface active agents (wetting agents, dispersing agents and/or emulsifying agents); solvents (water, or organic solvents such as aromatic solvents or chlorinated aliphatic solvents); adhesives, tnhickeners, binders; antifoaming agents; and other substances as mentioned herein. Solid carriers or diluents included in such compositions or formulations may include, for example, ground natural minerals such as kaolins, alumina, calcium carbonate, silica, kieselguhr, clay, etc.; ground synthetic materials such as various silicates and aluminosilicates and ground vegetable products such as bark, cornmeal, sawdust, cellulose powder and the like.

To manufacture solid compositions, the active substances are mixed with solid carriers or diluents such as those mentioned above and the mixture is ground to the appropriate size. Granules can be manufactured by dissolving an active compound in an organic solvent and applying the mixture, for example, by atomization, onto an absorptive granulated inert material, such as silica. Adhesives may be utilized to assist in the incorporation of the compound onto the solid particles. Pellets or granules can be manufactured by extrusion with appropriate carriers and binders.

Wettable powders, flowables, and pastes are obtained by mixing and grindingan active compound with one or more dispersing agents and/or solid carriersor diluents. Also included may be wetting agents and/or dispersing agents, for example, lignins, methyl cellulose, naphthalenesulfonic acid derivatives, fatty alcohol sulfates and various types of alkali and alkaline earth metal salts of fatty acids.

Emulsifiable concentrates are generally obtained by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, xylenes, or higher boiling aromatic hydrocarbons. To obtain suspensions oremulsions in water, wetting agents are generally also added.

It is possible to use highly concentrated liquid compositions containing upto about 95% by weight of the active compound, or even the active compound alone for those compounds which are liquids, when applying the compound inthe form of a finely divided liquid by use of various atomizing equipment, for example by airplane crop spraying techniques. For other purposes, however, the various types of compositions which can be utilized for thesecompounds will contain varying amounts of the compound according to the type of composition and the intended use.

In general, compositions may contain from 0.1 to 95% of the active compound, more preferably from 0.5 to 90%. Some typical compositions will contain an active compound as follows: wettable powders, flowables and pastes--20 to 90% active compound; oil suspensions, emulsions, solutions and emulsifiable concentrates--5 to 90% active compound; aqueous suspensions--10 to 50% active compound; dusts and powders--1 to 25% activecompound; granules and pellets--1 to 20% active compound.

The rate of application of the active compound to a locus to be controlled will depend on the activity of the compound and/or composition and the nature of the seeds and plants to be controlled and will vary from about 0.05 to about 50 pounds per acre (about 0.06 to about 56 kg/ha).

In addition to the active compound and the various agents utilized in preparing compositions and formulations mentioned above, such compositionsmay also contain one or more other active compounds of the type mentioned herein as well as other pesticidal agents, such as herbicides, fungicides,insecticides, acaricides, nematocides, bactericides, and plant growth regulators. Such compositions may also contain soil disinfectants or fumigants and may further contain fertilizers, thus making it possible to provide multi-purpose compositions containing one or more of the compoundsdescribed herein as well as, optionally, other pesticides and also fertilizers, all intended and formulated for use at the same locus.

Compositions containing one or more of the active compounds described, in aherbicidally effective amount, may be applied to the plant or locus to be controlled in any conventional manner. Thus, powders and various liquid compositions containing the active compound can be applied by the use of power dusters, boom and hand sprayers and spray dusters, or applied from airplanes as mists or sprays. When applied in the latter method they may be effective in very low dosages. To modify or control growth of germinating seeds or emerging seedlings liquid compositions may be appliedto the soil with conventional methods and may be distributed in the soil toa depth of one-half inch below the soil surface. The compositions need not be admixed with the soil particles but can be applied merely by sprinklingon the surface of the soil.

Compositions including active compounds may also be applied by addition to irrigation waters supplied to the field to be treated. This method of application permits penetration of the compounds into the soil as the water is absorbed therein.

EXAMPLES OF TYPICAL COMPOSITIONS

______________________________________OilIngredient           Weight %______________________________________Active Compound      1Oil solvent-heavy aromatic naphtha                99Total                100______________________________________Emulsifiable ConcentrateActive Compound      50Kerosene             45Emulsifying agent (mixture of longchain ethoxylated polyethers withlong chain sulfonate)                5Total                100______________________________________Emulsifiable ConcentrateActive Compound      90Kerosene             5Emulsifying agent (mixture of longchain ethoxylated polyethers withlong chain sulfonate)                5Total                100______________________________________Dusts and/or PowdersIngredient        Wt. %    Wt. %    Wt. %______________________________________Active Compound   0.5      50.0     90.0Attapulgite Clay Powder             93.5     44.0     4.0Sodium lignin sulfonate             5.0      5.0      5.0Sodium dioctyl sulfosuccinate             1.0      1.0      1.0Total             100.0    100.0    100.0______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4181001 *Mar 30, 1978Jan 1, 1980Vyzkumny Ustav Tvarecich Stroju A Technologie TvareniCross wedge rolling apparatus
JPS6341471A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5240918 *Mar 24, 1992Aug 31, 1993Egis Gyogyszergyar2-(substituted imino)-thiazolidines and process for the preparation thereof
US5292715 *Aug 28, 1992Mar 8, 1994Sumitomo Chemical Company, LimitedIminothiazolines, their production and use as herbicides
US5312798 *Sep 11, 1992May 17, 1994Sumitomo Chemical Company, LimitedHerbicidal composition
US5349788 *Oct 14, 1993Sep 27, 1994Saechsishe Werkzeug Und Sondermaschinen GmbhApparatus for catching residual water jet in water jet cutting apparatus
Classifications
U.S. Classification504/252, 548/196, 504/170, 548/195, 504/266, 504/179, 504/178, 504/167
International ClassificationA01N43/78, C07D417/12, A01N47/18, C07D277/20, A01N47/22, A01N53/00, A01N47/36
Cooperative ClassificationC07D417/12, A01N47/18, A01N47/36, A01N47/22, A01N53/00, A01N43/78, C07D277/20
European ClassificationA01N47/22, A01N47/18, A01N43/78, A01N47/36, C07D277/20, A01N53/00, C07D417/12
Legal Events
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Nov 20, 2001FPExpired due to failure to pay maintenance fee
Effective date: 20010919
Sep 16, 2001LAPSLapse for failure to pay maintenance fees
Apr 10, 2001REMIMaintenance fee reminder mailed
Mar 6, 1997FPAYFee payment
Year of fee payment: 8
Feb 22, 1993FPAYFee payment
Year of fee payment: 4
Aug 18, 1989ASAssignment
Owner name: ICI AMERICAS INC., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:STAUFFER CHEMICAL COMPANY DIVISION OF RHONE-POULENC, INC.;REEL/FRAME:005184/0165
Effective date: 19890815
May 22, 1989ASAssignment
Owner name: ICI AMERICAS INC., A CORP. OF DE., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WOOLARD, FRANK X.;REEL/FRAME:005072/0136
Effective date: 19890328